Crystalline forms of 4,4-bis-triazinylaminostilbene derivatives and processes for making same

ABSTRACT

For incorporation in detergents as optical brighteners, crystalline forms of the disodium salts of N,N&#39;&#39;-bis-(4-anilino-6( omega -alkoxyalkylamino)-1,3,5-triazin-2-yl)-4,4&#39;&#39;diaminostilbene-2,2&#39;&#39;-disulfonic acids having characteristic X-ray diffraction diagrams, are produced by converting yellow amorphous forms of the above compounds by crystallization from an aqueous solution having a pH higher than 7 and containing approximately 1.0 - 2.5 volume percent of a water-soluble electrolyte and the amorphous form at certain temperatures, or through heating and then cooling a mixture having a pH higher than 7 containing the amorphous form, water, a water-soluble electrolyte, and an inert water-soluble organic solvent.

United States Patent [1 1 Tscharner et al.

[ 4] CRYSTALLINE FORMS OF 4,4-BIS-TRIAZINYLAMINOSTILBENE DERIVATIVES AND PROCESSES FOR MAKING SAME [75] Inventors: Christopher Johannes Tscharner,

Warwick; Maurice Jacob Schwarz, Cranston, both of R.I.; Paul Horlacher, Mohlin, Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

22 Filed: Aug. 17,1973

[21] Appl. No.: 389,416

Related U.S. Application Data [63] Continuation of S81. No. 191494, Nov. 3, 1971, abandoned, which is a continuation of Ser. No. 814,562, April 9, 1969, abandoned.

[52] U.S. Cl 252/543; 252/301.2 W; 252/524; 260/240 B [51] Int. Cl. CllD 3/42; CO7D 251/68 [58] Field of Search 260/240 B; 252/543, 542, 252/524, 301.2 W

[56] References Cited UNITED STATES PATENTS 3,272.805 9/l966 Hausermann et a1 252/543 [451 Dec. 9, 1975 3,472,842 10/1969 Hausermann et a1 260/240 FOREIGN PATENTS OR APPLICATIONS 1,2|9,94O 6/1966 Germany 260/240 Primary ExaminerHerbert B. Guynn Attorney, Agent, or Firm-Joseph G. Kolodny; Edward McC. Roberts; Prabodh I. Almaula ABSTRACT For incorporation in detergents as optical brighteners, crystalline forms of the disodium salts of N,N'-bis-[4- anilino-6-(m-alkoxyalkylamino l ,3,5 -triazin-2-yl 4,4'-diaminostilbene-2,2'-disulfonic acids having char acteristic X-ray diffraction diagrams, are produced by converting yellow amorphous forms of the above compounds by crystallization from an aqueous solution having a pH higher than 7 and containing approximately 1.0 2.5 volume percent of a water-soluble electrolyte and the amorphous form at certain temperatures, or through heating and then cooling a mixture having a pH higher than 7 containing the amorphous form, water, a water-soluble electrolyte, and an inert water-soluble organic solvent.

2 Claims, 4 Drawing Figures US. Patent Dec. 9, 1975 Sheet 1 of 4 3,925,260

mw WI \& mm Q I IN VEN TOR.

US. Patent Dec. 9, 1975 Sheet 2 of4 3,925,260

AN l l l u I N VEN TOR.

lll

I N VEN TOR.

I I LN I N VEN TOR.

product itself is white compared to the generally yel- CRYSTALUNE FORMS OF lowish color of the amorphous form. This feature is es- 4,4-BIS-TRIAZINYLAMINOSTILBENE pecially advantageous in detergents since no unwanted DERWATIVES AND PROCESSES FOR MAKING color shades are thus imparted to the detergent powder SAME 5 by the brightener.

This is a continuation of application Scr. NO. These new crystalline products of the formulalcom 195,494, filed on Nov. 3, 1971, which in turn is a conpounds have specific X-ray diffraction diagrams. tinuation of application Ser. No. 814,562, filed on Apr. In one aspect, the crystalline products according to 9, I969 both now abandoned. the present invention have the following formula:

wherein DETAILED DISCLOSURE R is alkyl of from 1 to 2 carbon atoms,

The present invention pertains to new crystalline y is an integer of from 2 to 3 and forms of the disodium salt of N,N'-bis-[4-anilino-6-(w- X is approximately 7. alk0 y lkyl m .5- i zin-2-yll-4,4'- i The crystalline products of formula la, called the abenc-2,2'-disulfonic acid and to process O the pr pforms, are obtained by crystallization from an aqueous,

aration of such pI'OdUCtS and thfilf use as optical bl'lghtelectrolyte containing olution of a cgmpound of foreners in detergents. mula I. The solution has a pH higher than 7 and the Optical brighteners of the formula: temperature is maintained between 20 and 70C, pref- I H NflO S C N C N/0\CNH nc N HC=CH O C--N N-- C SO Na HN- (CH2 )v- R wherein erably between and 55C. In order to shorten the R is alkyl of from 1 to 2 carbon atoms and period for crystallization, it is advisable to add seed y is an integer of from 2 to 3 crystals. The preferred electrolyte is the sodium salt of are known, for instance, from Swiss Pat. No. 386,436 a mineral acid, especially sodium chloride. The amount and US. Pat. No. 3,272,805. of electrolyte employed ranges from 1.0 to 2.5% by vol- The products obtained according to the known proume and is preferably 1.5 to 2.0%. cesses are yellow and amorphous; they are readily solu- Since the new crystalline forms are only slightly ble in water and can easily be incorporated into deterwater-soluble, they are obtained in good yields and are gents. However, these amorphous products still contain very pure. Impurities such as, poly-4,4'-diuminosti|- impurities and products of side reactions. Such impuribene-2,2'-disulfonic acid, hydroxy-, tetraalkties and by-products are detrimental; they can be reanolamino-, and trialkanolamino compounds, all of moved if at all only by extensive work-up procewhich are formed during the preparation of compounds dures which also entail the loss of the desired product. of formula l, remain dissolved and can be removed eas- According to the present invention, it is now surprisily by washing. ingly possible to produce crystalline forms of the com- The pure, crystalline products can be dried in vacuo pounds of formula I, which show less water-solubility at 2535C without changes in crystal form. If the and accordingly can be prepared as very pure products. freshly prepared products of formula la are dried be- The crystalline forms of this invention give better optitween 40 and 80C, there is a change in crystal forms cal brightening effects than equal amounts of the through loss of crystal water, but this process is reversknOWn ph Crude PO t o e. ible by subsequent absorption of water. On heating the greater maximal brightening effect can be achieved and products of formula (la at temperatures above [00C, in the case of the products of Formula lb below the an amorphous form is obtained which cannot be recon- 3,925,260 3 4 verted into a crystalline form by absorption of water. either of the two above-described processes show gooc This amorphous form which is obtained, however. is afinity to cellulose fibers upon application by the usua suitable for incorporation into textile detergents due to methods. They draw onto the fibers at low temperaitS Weaker COlOr H OPPOS d ID les Pu a 'Ph tures, i.e. temperatures between about 3S60C anc fon'ns. 5 are, therefore, suitable for the household laundry.

Alternatively, other crystalline forms, called the [3- Of particular importance are the crystalline products forms, with less crystal water can be obtained by crysof formula la (the a-forms) and lb (the B-formsj tallizing from a mixture consisting of water, a water-solwherein R is methyl and y is 2 or 3.

uble electrolyte, an inert and at least partially water- FIGS. l4 are X-ray diffraction diagrams of the presoluble organic solvent, and a compound of formula I, ll ferred crystalline forms, respectively, of formula [0 which mixture has a pH higher than 7. by heating to rewhere R is methyl, X is 7 and y is 3 and 2 and formula flux, and then distilling off the organic solvent. A prodlb where R is methyl, X is l, and y is 3 and 2. The act of the following formula crystallizes in the form of above-described preferred species of formulas Ia and [Z thermostable crystals. and is called the B-form: are set out below as formulas IlV.

NH uu@ l uao s g h i The X-ray diffraction diagrams characteristic ol these products are produced by means of a counter goniometer made by Philips, Eindhoven, using CuK a radiation. The instrument records the intensity of the diffracted ray along the vertical axis in relation to the R is alkyl of from I to 2 carbon atoms, y is an integer of from 2 to 3 and 3( X is either 1 or 2.

It is also advantageous to accelerate the crystallizadiffraction angle 2 6. The jnterplanar spacings d are tion in this process with seed crystals. Preferred organic q ntly Calculated in Angstrt'im from the diffracsolvents are ketones, for example, acetone, and prefertion angles by using the Bragg equation n. )t 2d. sin 0. ably methylethylketone. The preferred water-soluble 35 The accuracy is to about 0. 1. This should be taken into electrolyte is a sodium salt of a mineral acid, preferably consideration in the interpretation of the data. sodium chloride. The concentration of the electrolyte The crystalline form of the compound of formula ll,

is preferably 23-35%, by weight, calculated on the the a-form,

ca e-(ca -NH HN (CH2 )3 0 CH3 amount of water. The mixture is preferably heated to is characterized by the X-ray diffraction diagram of boiling under reflux and is kept at this temperature for FIG. I which shows the following characteristic lines: a

a period of time, generally from about one to two very strong line at 2 0= 3.9 and two fairly strong lines hours. The organic solvent is then removed by distilla- 55 at 16.23 and 23.85.

The crystalline form of the compound of formula Ill,

tion.

The crystalline products prepared in accordance with the a-form,

n O C-Nll ncaca Q Nil-C O N 7 H2 c N N C l O Na (III) uao s is characterized by the X-ray diffraction diagram of FIG. 3 with the following characteristic lines: a very strong line at 2 6.48", a strong line at 23.39 and two fairly strong lines at l9.72 and 24.2".

The crystalline form of the compound of formula V, the B-form,

NELO S N O C-NH HC=CH o l SO N CH -O-(CHz lama is characterized by the X-ray diffraction diagram of FIG. 4 with the following characteristic lines: a strong line at 2 6 40 and two fairly strong lines at 625 and 45 EXAMPLE I a. A suspension of I00 g of cyanuric chloride in a mixture of 300 ml of water and 700 g of ice is prepared.

i200 ml of an aqueous solution containing 100 g of 55 4,4'-diaminostilbene-2,2-disulfonic acid sodium salt and 29 g of sodium carbonate are slowly added while stirring within 1 to 3 hours at a temperature of 0 to 5C and the reaction mixture is subsequently stirred for another few minutes. Then, 50 g of aniline are added and the pH of the reaction mixture adjusted to 7 to 9 by means of a sodium hydroxide solution keeping the temperature at 2-25C. After the substitution reaction is terminated, which is evident from a negative reaction for aniline, for example, by diazotization, i.e. after about I hour, 58 g of 3-methoxy propylamine are added and the reaction mixture is heated to boiling. The pH value of the reaction mixture is kept at 10 to 1 l 6 by addition of sodium hydroxide solution. After the reaction has been completed, the reaction mixture IS cooled to 50C. The reaction mixture contains crude disodium salt of N,N'-bis-[4-anilino-6-(3-methoxy propylamino)-1 ,3,5-triazin-2-yl]-4,4'-diaminostilbene- 2,2'-disulfonic acid.

b. Water is added to the inhomogeneous reaction mixture containing the crude disodium salt of N,N'-bis- [4-anilino-6-( 3-methoxy propylamino l ,3,5-triazin-2- yl]-4,4'-diaminostilbene-2,2'-disulfonic acid until a sodium chloride concentration of 1.5% by volume is obtained. Seed crystals of the same product containing 7 NH-C ii 1 H O mr- (c14 -o-ca moles of crystal water per mole of product are added and the reaction mixture stirred at 4555C until the crystallization which starts immediately is completed. Then the mixture is cooled to to C. The crystals are removed by filtration and washed with l.5% by volume sodium chloride solution. After drying, pure white crystals of the compound of the a-form, are obtained.

The yield is 9l% of the theory. The product is suitable for incorporation into textile detergents.

A product almost as pure as the one obtained above is also obtained when the crystals are carefully filtered oh by suction and are not washed with a sodium chloride solution.

EXAMPLE 2 a. A suspension is prepared from I00 g of cyanuric chloride, 300 ml of water and 700 g of ice. To this suspension are slowly added I200 ml of an aqueous solution of 100 g of 4,4'-diaminostilbene-2,2-disulfonic acid sodium salt and 29 g of sodium carbonate at a temperature of 0-5C withstirring. Subsequently, g of aniline are added and the reaction mixture is adjusted to a pH of 7 to 9 by means of a sodium hydroxide solution keeping the temperature between 2 and 25C. After the substitution is completed, 58 g of 3-methoxy propylamine are added and the reaction mixture is heated to boiling. The pH of the reaction mixture is kept at pH -1 1 by means of a sodium hydroxide solution; reaction is completed, the reaction then, after the mixture is cooled to 60 to 65C. The highly concentrated, aqueous solution of the optical brightener is separated from the top brine layer and is dissolved in 1800 ml of water at 50C. The reaction mixture is then filtered. The clear filtrate is slowly added to a mixture of 600 g of sodium chloride and 400 ml of water which is at a temperature of 50C. The amorphous form of N.N-bis-[4-anilino-6-(3'methoxy propylamino)l ,3,5- triazin-2-y1]-4.4-diaminostilbene-2,2disulfonic acid disodium salt is filtered off and is used for the following step.

b. Moist or dry, crude, amorphous N,N'-bis-[4- anilino-6-( 3-methoxy propylamino)-1,3,5-triazin-2-yl]- 4,4-diaminostilbene-2,2'-disulfonic acid disodium salt is dissolved in 2000 ml of water. The sodium chloride concentration is adjusted to between 1.0% to 1.2% by volume. Seed crystals of the above-described compound having 7 moles of water incorporated per mol are added and the reaction mixture is stirred at 4555 until crystallization is completed after about 3 to 8 hours. The mixture is cooled to 20-35, the crystals separated by filtration and washed with 1.5% by volume of sodium chloride solution. After drying, pure, white crystals of the compound of formula 11, the aform, are obtained in a 89% yield.

Relatively pure crystals are also obtained when the crystals are carefully filtered off by suction but are not washed with a sodium chloride solution.

EXAMPLE 3 The starting solution containing crude N,N'-bis-[4- anilino-6-( 3-methoxy propy1amino)- l ,3,5-triazin-2-yl]- 4,4-diaminostilbene-2,2-disulfonic acid disodium salt is obtained by separation of the highly concentrated aqueous reaction solution containing the crude product from the top brine layer as outlined in Example 2a. The highly concentrated solution is poured into 1800 ml of water of 50C and clarified. 30 g of sodium sulfate are added, and the solution obtained is used as starting material for the following step.

The solution obtained is treated as described in Example lb. Pure, white crystals of the compound of formula 11, the a-form, are obtained in 90% yield.

EXAMPLE 4 a. A suspension is prepared from 100 g of cyanuric chloride, 300 ml of water and 700 g of ice. A solution of 100 g of 4,4-diaminostilbene-2,2'-disulfonic acid sodium salt in 800 ml of water is slowly added while stirring at a temperature of 05C keeping the pH value at between 4 and 6 by simultaneously adding a by volume of sodium carbonate solution. Subsequently, 50 g of aniline are added at a temperature of between 2C and 25C and the pH is adjusted to 7 to 9 by means of a sodium hydroxide solution. After substitution is completed, 49 g of 2-methoxy ethylamine are added and the reaction mixture is heated to boiling. The pH value is adjusted to 10 to l l by means of a sodium hydroxide solution. The reaction mixture is cooled to 50C and is used as starting material for the following step.

b. To the inhomogeneous, aqueous reaction mixture of (0) containing crude N,N-bis-[4-anilino-6-(2- methoxy ethylamino l ,3,5-triazin-2-yl ]-4.4 diaminostilbene-2,2'-disulfonic acid disodium salt water is added until a sodium chloride concentration of 2.0% by volume, is obtained. Seed crystals of the compound containing 7 moles of crystal water per mol of compound are added and the reaction mixture is stirred at 45- 55 until the starting crystallization which starts immediately is completed. The mixture is cooled to 20C to 35C and the crystals are filtered off. After drying, pure, yellow crystals of the compound of formula III, the a-form, are obtained in a yield of 91% of the theory.

On heating this product to a temperature above 100C a water-free, amorphous product is obtained which is suitable for incorporation into textile detergents due to its purity and excellent water-solubility.

EXAMPLE 5 a. The starting material is prepared according to Example 4a. However, after the substitution reaction is completed, 40 g of sodium chloride are added and the reaction mixture is cooled to 60 to 65C. The highly concentrated aqueous solution of the optical brightener is separated from the top brine layer, and is poured into 1800 ml of water of a temperature of 50C and then clarified. The clear filtrate is slowly added to a mixture of 400 ml of water and 600 g of sodium chloride, said mixture having a temperature of 50C. The amorphous form of the desired product is isolated and used for the next step.

b. Moist or dry, crude, amorphous N,N'-bis-[4- anilino-6-(3-methoxy ethylamine)-l ,3,5-triazin-2-yl]- 4,4-diaminostilbene-2,2'-disulfonic acid disodium salt obtained as described above, is dissolved in 2000 m1 of water. The sodium chloride concentration is adjusted to 2 to 2.5% by volume. Seed crystals of the abovementioned compound containing 7 moles of crystals water per mol of compound are added and the reaction mixture is stirred at 45C to 55C until the crystallization which starts immediately is completed after a period of 4 to 8 hours. The mixture is cooled to 20C to 35C and the crystals are filtered off. After drying, pure, yellow crystals of the compound of formula 11!, the a-form, are obtained in a yield of 89% of the theory.

EXAMPLE6 a. The optical brightener is prepared according to Example 4a. However, after the substitution reaction has been completed, 40 g of sodium chloride are added and the mixture is cooled to 60C to 65C. The crude product in fonn of a highly concentrated aqueous solution is separated from the top brine layer and is poured into 1800 ml of water having a temperature of 50C. The solution is clarified and 50 g of sodium sulfate are added to the clear filtrate. The filtrate containing the desired crude N,N '-bis-[4-anilino-6-( 2-methoxy ethylamino l ,3,5-triazin-2-yl ]-4,4 '-diaminostilbene- 2,2'-disulfonic acid disodium salt is used for the next step.

b. The reaction mixture prepared above is treated as described in Example 4b. Pure, yellow crystals of the compound of fonnula 111, the a-form, are obtained in a yield of 90% of the theory.

EXAMPLE 7 In a 1 liter flask equipped with stirrer, thermometer, reflux condenser, and funnel tube, there is placed 50 g of amorphous N .N -bis-[4anilino-6-( 3-methoxy propylamino l ,3,S-triazin-Z-yll-4,4'-diaminostilbene 2,2'-disulfonic acid disodium salt, 375 g of hot water, and I60 g of methylethylketone. The mixture is heated to 70C while stirring and the pH is adjusted to ll with a 50% alkali hydroxide solution. 150 g of sodium chloride are added; the mixture is heated to reflux temperature (74C and is kept at this temperature for approximately 1 hour. By gradually raising the temperature, the methylethylketone is distilled off. At 85C, some product precipitates in lumps which disintegrate after the complete removal of the methylethylketone, forming a highly fluid crystal slurry. When the temperature has reached lC and the methylethylketone has been removed, the mixture is cooled to room temperature while stirring. The product is filtered off and is washed with 500 g of a trisodiumphosphate solution and 200 g of a sodium chloride solution. The liquid is removed by suction and the moist cake obtained is dried in vacuo at 100C. 60 g pure, white crystals of the compound of formula IV, the B-form, are obtained.

This crystalline form is suitable for the incorporation into textile detergents.

EXAMPLE 8 The compound of formula V, the B-form, is prepared according to Example 7, however, instead of amorphous N,N'-bis-[4-anilino-6-(3-methoxy propylamino)-l ,3,5-triazin-2-yl]- 4,4'-diaminostilbene-2,2'-disulfonic acid disodium salt, N,N'-bis-[4-anilino-( 2-methoxy ethylamino )-1 ,3,5- triazin-Z-yl ]-4,4 '-diaminostilbene-2,2 '-disulfonic acid disodium salt is used. 60 g of pure, white crystals of the compound of formula V, the B-form, are obtained. This compound is suitable for the incorporation into textile detergents.

EXAMPLE 9 A suspension of 63.75 g of cyanuric chloride in a mixture of 500 g of crushed ice and 500 g of methylethylketone is prepared in a 3 liter flask. 658 g of a l0% clear, amber disodium diaminostilbene disulfonate solution of 64 g of diaminostilbene disulfonic acid containing 18 g of sodium carbonate at 20-25C is added over a period of 50 minutes. The pH is maintained at 4-5 and the reaction temperature maintained below 5C while stirring is continued for approximately 1 hour. There is then added 32.35 g of aniline. The pH is maintained at 67.5 by addition of a 50% solution of sodium hydroxide. The reaction is continued at about 50C for about 1 hour. After this substitution reaction is completed, which is indicated by a negative reaction for aniline, 45 g of 65% of Z-methoxy ethylamine are added and the reaction mixture heated to 65C and maintained at a pH of [0.5-1 1 by the gradual addition of the 50% solution of sodium hydroxide. The temperature is maintained at 65C for 30 minutes. After completion of the reaction, 400 g of sodium chloride are added and the reaction mixture is heated at reflux for 1 hour. The methylethyl ketone is then distilled at 90C, whereupon the compound of formula V, the B-form, begins to crystallize. The reaction temperature is then raised to 97C distilling off the remainder of the methylethylketone. The mixture is then cooled to room temperature with stirring and the liquid removed and the product filtered off. The product is dried at 100C in a vacuum. l75-l 85 g of pure, white crystals of the compound of formula V, the B-form, are obtained. This crystalline form is suitable for incorporation into textile detergents.

10 in each of the foregoing examples, the structures of the compound is confirmed by determination of X-ray diffraction patterns.

EXAMPLE l0 0.25 g Of the crystalline optical brightener of formula [I obtained according to Examples l, 2 or 3 are dissolved in 2.5 ml of 1N sodium hydroxide solution and l00 ml of water and then worked up into a homogeneous paste with I00 g of a heavy duty detergent consisting of:

I52 parts of sodium dodecylbenzene sulfonate,

3.8 parts of sodium lauryl sulfate,

25.6 parts of sodium tripolyphosphate,

7.6 parts of tetrasodium pyrophosphate,

4.8 parts of sodium silicate,

1.9 parts of magnesium silicate,

5.0 parts of sodium carbonate,

1.4 parts of carbomethyl cellulose,

0.3 parts of sodium salt of ethylenediamine tetra acetic acid, and

34.4 parts of sodium sulfate The mixture is then dried at C, crushed and finally pressed through a sieve.

The washing powder obtained has a high degree of whiteness and very effectively brightens a mixed load of household laundry.

EXAMPLE 1 I if the procedure given in Example I0 is followed, however, replacing the g of detergent by another heavy duty detergent consisting of 7.8 parts of sodium lauryl sulfate, 1 1.0 parts of sodium dodecylbenzene sulfonate, I I0 parts of sodium tripolyphosphate, l6.6 parts of tetrasodium pyrophosphate, 4.6 parts of sodium silicate, l.4 parts of carbomethyl cellulose, 36.8 parts of sodium sulfate, and 8.0 parts of sodium perborate (NaBo 4 H O) a washing agent is obtained having a high degree of whiteness.

EXAMPLE 12 A composition consisting of 5l parts of sodium-n-dodecylbenzene sulfonate,

24 parts of sodium xylene sulfonate,

l0 parts of nonylphenoxy polyoxyethylene ethanol,

7 parts of lauroyl diethanol amide, and

8 parts of water is intimately mixed with a solution of 0.2 parts of the crystalline optical brightener of formula 1]] described in Examples 4 to 6 in 100 parts of water and 2 parts of l N sodium hydroxide solution. The mixture is dried at 85C, crushed, and finally pressed through a sieve. An excellent detergent, particularly suitable for household washing machines, is obtained.

EXAMPLE l3 A composition consisting of 24 parts of nonylphenol polyethyleneglycolether,

25 parts of sodium tripolyphosphate,

5 parts of disodium phosphate,

25 parts of sodium carbonate, and

25 parts of sodium chloride, is intimately mixed with 0.5 parts of the thermostable optical brightener of formula IV of Example 7 in a ribbon blender for 6 minutes. A detergent is obtained hav- 11 12 ing a high degree of whiteness and which imparts a high 933, 200, 25 and 26 42 degree o b gh ne I te t l Washed n- 2. A composition of matter consisting essentially 01 What is claimed is: an anionic detergent and an amount sufficient to iml. A composition of matter consisting essentially of part optical brightening thereto of the a-crystalline an anionic detergent and an amount sufficient to imform of a compound having the formula:

@NH HN@ l NaO s l c \r 1 /N C\ N f-NH C=C NH-C 0 N 7 H O C N l N- C l so na HN- (cH -o-cn part optical brightening thereto of the a-crystalline cterised by an X-ray diffraction pattern having form of a compound having the formuh: the following characteristics lines corresponding to: a

3 1 mo s i (/N c N ON/C-NH HC=C NH- O N 7 H f N C so Na CH3 O (CH2 )rm 3 Hit-(ca -o-cn characterized by an X-ray diffraction pattern havmg very strong line at 3.9 and two falrly strong lines at the following characteristic lines corresponding to: a l6.23 and 23.85. very strong line at 3.42 and four fairly strong lines at 

1. A COMPOSITION OF MATTER CONSISTING ESSENTIALLY OF AN ANIONIC DETERGENT AND AN AMOUNT SUFFICIENT TO IMPART OPTICAL BRIGHTENING THERETO OF THE A-CRYSTALLINE FORM OF A COMPOUND HAVING THE FORMULA:
 2. A composition of matter consisting essentially of an anionic detergent and an amount sufficient to impart optical brightening thereto of the Alpha -crystalline form of a compound having the formula: 